This invention relates to hard surface cleaning products comprising particular types of improved alkylbenzene sulfonate surfactant mixtures adapted for use by controlling compositional parameters, especially a 2/3-phenyl index and a 2-methyl-2-phenyl index.
The developer and formulator of surfactants for hard surface cleaning must consider a wide variety of possibilities with limited (sometimes inconsistent) information, and then strive to provide overall improvements in one or more of a whole array of criteria, including performance in the presence of free calcium in complex mixtures of surfactants and polymers, e.g. cationic polymers, formulation changes, enzymes, various changes in consumer habits and practices, and the need for biodegradability.
Further, hard surface cleaning should employ materials that enhance the tolerance of the system to hardness, especially to avoid the precipitation of the calcium salts of anionic surfactants. Precipitation of the calcium salts of anionic surfactants is known to cause unsightly deposits on hard surfaces, especially dark hard surfaces. In addition, precipitation of surfactants can lead to losses in performance as a result of the lower level of available cleaning agent. In the context provided by these preliminary remarks, the development of improved alkylbenzene sulfonates for use in hard surface cleaning compositions is clearly a complex challenge. The present invention relates to improvements in such surfactant compositions.
It is an aspect of the present invention to provide mixtures of the modified alkylbenzene sulfonate surfactant mixtures which are formulatable to provide cleaning compositions having one or more advantages, including greater product stability at low temperatures, increased resistance to water hardness, greater efficacy in surfactant systems, filming and streaking, improved removal of greasy or particulate body soils, and the like.
U.S. Pat. Nos. 5,659,099, 5,393,718, 5,256,392, 5,227,558, 5,139,759, 5,164,169, 5,116,794, 4,840,929, 5,744,673, 5,522,984, 5,811,623, 5,777,187, WO 9,729,064, WO 9,747573, WO 9,729,063, U.S. Pat. Nos. 5,026,933; 4,990,718; 4,301,316; 4,301,317; 4,855,527; 4,870,038; 2,477,382; EP 466,558, Jan. 15, 1992; EP 469,940, 2/5/92; FR 2,697,246, Apr. 29, 1994; SU 793,972, Jan. 7, 1981; U.S. Pat Nos. 2,564,072; 3,196,174; 3,238,249; 3,355,484; 3,442,964; 3,492,364; 4,959,491; WO 88/07030, Sep. 25, 1990; U.S Pat. Nos. 4,962,256, 5,196,624; 5,196,625; EP 364,012 B, Feb. 15, 1990; U.S. Pat. Nos. 3,312,745; 3,341,614; 3,442,965; 3,674,885; 4,447,664; 4,533,651; 4,587,374; 4,996,386; 5,210,060; 5,510,306; WO 95/17961, Jul. 6, 1995; WO 95/18084; U.S. Pat. Nos. 5,510,306; 5,087,788; 4,301,316; 4,301,317; 4,855,527; 4,870,038; 5,026,933; 5,625,105 and 4,973,788. See Vol 56 in xe2x80x9cSurfactant Sciencexe2x80x9d series, Marcel Dekker, New York, 1996, including in particular Chapter 2 entitled xe2x80x9cAlkylarylsulfonates: History, Manufacture, Analysis and Environmental Propertiesxe2x80x9d, pages 39-108, xe2x80x9cSurfactant Sciencexe2x80x9d series, Vol 73, Marcel Dekker, New York, 1998 and xe2x80x9cSurfactant Sciencexe2x80x9d series, Vol 40, Marcel Dekker, New York, 1992. See also copending U.S. Patent applications No. 60/053,319 filed on Jul. 21, 1997, No. 60/053,318, filed on Jul. 21, 1997, No. 60/053,321, filed on Jul. 21, 1997, No. 60/053,209, filed on Jul. 21, 1997, No. 60/053,328, filed on Jul. 21, 1997, No. 60/053,186, filed on Jul. 21, 1997 and the art cited therein. Documents referenced herein are incorporated in their entirety.
The present invention provides a hard surface cleaning compositions comprising a modified alkylbenzene sulfonate surfactant mixtures and a conventional surface cleansing additive.
Specifically, the first embodiment of the present invention comprises a hard surface cleaning composition comprising:
(i) from about 0.01% to about 95% by weight of composition of a modified alkylbenzene sulfonate surfactant mixture comprising:
(a) from about 15% to about 99% by weight of surfactant mixture, a mixture of branched alkylbenzene sulfonates having formula (I): 
xe2x80x83wherein L is an acyclic aliphatic moiety consisting of carbon and hydrogen, said L having two methyl termini and said L having no substituents other than A, R1 and R2; and wherein said mixture of branched alkylbenzene sulfonates contains two or more of said branched alkylbenzene sulfonates differing in molecular weight of the anion of said formula (I) and wherein said mixture of branched alkylbenzene sulfonates has
a sum of carbon atoms in R1, L and R2 of from 9 to 15;
an average aliphatic carbon content of from about 10.0 to about 14.0 carbon atoms; M is a cation or cation mixture having a valence q; a and b are integers selected such that said branched alkylbenzene sulfonates are electroneutral; R1 is C1-C3 alkyl; R2 is selected from H and C1-C3 alkyl; A is a benzene moiety; and
(b) from about 1% to about 85% by weight of surfactant mixture, of a mixture of nonbranched alkylbenzene sulfonates having formula (II): 
xe2x80x83wherein a, b, M, A and q are as defined hereinbefore and Y is an unsubstituted linear aliphatic moiety consisting of carbon and hydrogen having two methyl termini, and wherein said Y has a sum of carbon atoms of from 9 to 15, preferably from 10 to 14, and said Y has an average aliphatic carbon content of from about 10.0 to about 14.0; and
wherein said modified alkylbenzene sulfonate surfactant mixture is further characterized by a 2/3-phenyl index of from about 160 to about 275;
(ii) from about 0.001% to 99.9% by weight of a conventional surface cleansing additive;
wherein said composition is further characterized by a 2/3-phenyl index of from about 160 to about 275.
Specifically, the second embodiment of the present invention comprises a hard surface cleaning composition comprising:
(i) a modified alkylbenzene sulfonate surfactant mixture comprising the product of a process comprising the steps of:
(I) alkylating benzene with an alkylating mixture in the presence of a zeolite beta catalyst;
(II) sulfonating the product of (I); and
(III) neutralizing the product of (II);
wherein said alkylating mixture comprises:
(a) from about 1% to about 99.9%, by weight of alkylating mixture of branched C9-C20 monoolefins, said branched monoolefins having structures identical with those of the branched monoolefins formed by dehydrogenating branched paraffins of formula R1LR2 wherein L is an acyclic aliphatic moiety consisting of carbon and hydrogen and containing two terminal methyls; R1 is C1 to C3 alkyl; and R2 is selected from H and C1 to C3 alkyl; and
(b) from about 0.1% to about 85%, by weight of alkylating mixture of C9-C20 linear aliphatic olefins;
wherein said alkylating mixture contains said branched C9-C20 monoolefins having at least two different carbon numbers in said C9-C20 range, and has a mean carbon content of from about 9.0 to about 15.0 carbon atoms; and wherein said components (a) and (b) are at a weight ratio of at least about 15:85;
(ii) from about 0.001% to 99.9% by weight of a conventional surface cleansing additive,
wherein said composition is further characterized by a 2/3-phenyl index of from about 160 to about 275.
Specifically, the third embodiment of the present invention comprises a hard surface cleaning composition comprising:
(i) a modified alkylbenzene sulfonate surfactant mixture consisting essentially of the product of a process comprising the steps, in sequence, of:
(I) alkylating benzene with an alkylating mixture in the presence of a zeolite beta catalyst;
(II) sulfonating the product of (I); and
(III) neutralizing the product of (II);
wherein said alkylating mixture comprises:
(a) from about 1% to about 99.9%, by weight of alkylating mixture of a branched alkylating agent selected from the group consisting of:
(A) C9-C20 internal monoolefins R1LR2 wherein L is an acyclic olefinic moiety consisting of carbon and hydrogen and containing two terminal methyls;
(B) C9-C20 alpha monoolefins R1AR2 wherein A is an acyclic alpha-olefinic moiety consisting of carbon and hydrogen and containing one terminal methyl and one terminal olefinic methylene;
(C) C9-C20 vinylidene monoolefins R1BR2 wherein B is an acyclic vinylidene olefin moiety consisting of carbon and hydrogen and containing two terminal methyls and one internal olefinic methylene;
(D) C9-C20 primary alcohols R1QR2 wherein Q is an acyclic aliphatic primary terminal alcohol moiety consisting of carbon, hydrogen and oxygen and containing one terminal methyl;
(E) C9-C20 primary alcohols R1ZR2 wherein Z is an acyclic aliphatic primary nonterminal alcohol moiety consisting of carbon, hydrogen and oxygen and containing two terminal methyls; and
(F) mixtures thereof;
wherein in any of (A)-(F), said R1 is C1 to C3 alkyl and said R2 is selected from H and C1 to C3 alkyl; and
(b) from about 0.1% to about 85%, by weight of alkylating mixture of C9-C20 linear alkylating agent selected from C9-C20 linear aliphatic olefins, C9-C20 linear aliphatic alcohols and mixtures thereof;
wherein said alkylating mixture contains said branched alkylating agents having at least two different carbon numbers in said C9-C20 range, and has a mean carbon content of from about 9.0 to about 15.0 carbon atoms; and
wherein said components (a) and (b) are at a weight ratio of at least about 15:85;
(ii) from about 0.001% to 99.9% by weight of a conventional surface cleansing additive;
wherein said composition is further characterized by a 2/3-phenyl index of from about 160 to about 275.
Specifically, the fourth embodiment of the present invention comprises a hard surface cleaning composition comprising:
(i) from about 0.01% to about 95% by weight of composition of a modified alkylbenzene sulfonate surfactant mixture comprising:
(a) from about 15% to about 99% by weight of surfactant mixture, a mixture of branched alkylbenzene sulfonates having formula (I): 
xe2x80x83wherein L is an acyclic aliphatic moiety consisting of carbon and hydrogen, said L having two methyl termini and said L having no substituents other than A, R1 and R2; and wherein said mixture of branched alkylbenzene sulfonates contains two or more of said branched alkylbenzene sulfonates differing in molecular weight of the anion of said formula (I) and wherein said mixture of branched alkylbenzene sulfonates has
a sum of carbon atoms in R1, L and R2 of from 9 to 15;
an average aliphatic carbon content of from about 10.0 to about 14.0 carbon atoms; M is a cation or cation mixture having a valence q; a and b are integers selected such that said branched alkylbenzene sulfonates are electroneutral; R1 is C1-C3 alkyl; R2 is selected from H and C1-C3 alkyl; A is a benzene moiety; and
(b) from about 1% to about 85% by weight of surfactant mixture, of a mixture of nonbranched alkylbenzene sulfonates having formula (II): 
xe2x80x83wherein a, b, M, A and q are as defined hereinbefore and Y is an unsubstituted linear aliphatic moiety consisting of carbon and hydrogen having two methyl termini, and wherein said Y has a sum of carbon atoms of from 9 to 15, preferably from 10 to 14, and said Y has an average aliphatic carbon content of from about 10.0 to about 14.0; and
wherein said modified alkylbenzene sulfonate surfactant mixture is further characterized by a 2/3-phenyl index of from about 160 to about 275 and wherein said modified alkylbenzene sulfonate surfactant mixture has a 2-methyl-2-phenyl index of less than about 0.3;
(ii) from about 0.001% to 99.9% by weight of a conventional surface cleansing additive; and
(iii) from about 0.00001% to about 99.9% of composition of a surfactant selected from the group consisting of anionic surfactants other than those of (i), nonionic surfactants, zwitterionic surfactants, cationic surfactants, amphoteric surfactant and mixtures thereof;
provided that when said detergent composition comprises any alkylbenzene sulfonate surfactant other than said modified alkylbenzene sulfonate surfactant mixture, said detergent composition is further characterized by an overall 2/3-phenyl index of at least about 160, wherein said overall 2/3-phenyl index is determined by measuring 2/3-phenyl index, as defined herein, on a blend of said modified alkylbenzene sulfonate surfactant mixture and said any other alkylbenzene sulfonate to be added to said detergent composition, said blend, for purposes of measurement, being prepared from aliquots of said modified alkylbenzene sulfonate surfactant mixture and said other alkylbenzene sulfonate not yet exposed to any other of said components of the detergent composition; and further provided that when said detergent composition comprises any alkylbenzene sulfonate surfactant other than said modified alkylbenzene sulfonate surfactant mixture, said detergent composition is further characterized by an overall 2-methyl-2-phenyl index of less than about 0.3, wherein said overall 2-methyl-2-phenyl index is to be determined by measuring 2-methyl-2-phenyl index, as defined herein, on a blend of said modified alkylbenzene sulfonate surfactant mixture and any other alkylbenzene sulfonate to be added to said detergent composition, said blend, for purposes of measurement, being prepared from aliquots of said modified alkylbenzene sulfonate surfactant mixture and said other alkylbenzene sulfonate not yet exposed to any other of said components of the detergent composition.
In a fifth embodiment the present invention also includes a method of cleaning a hard surface by administering an effective amount of a hard surface cleaning composition as hereinbefore defined.
In a sixth embodiment the present invention also includes a method for cleaning a hard surface by administering an effective amount of a diluted aqueous solution of the hard surface cleaning compositions as hereinbefore defined.
In a seventh embodiment, the present compositions (according to any of the present compositional embodiments) can be used in combination with an implement for cleaning a surface, the implement preferably comprising:
a. a handle; and
b. a removable cleaning pad comprising a suberabsorbent material and having a plurality of substantially planar surfaces, wherein each of the substantially planar surfaces contacts the surface being cleaned, and preferably a pad structure which has both a first layer and a second layer, wherein the first layer is located between the scrubbing layer and the second layer and has a smaller width than the second layer.
Depending on the means used for attaching the cleaning pad to the cleaning implement""s handle, it may be preferable for the cleaning pad to further comprise a distinct attachment layer. In these embodiments, the absorbent layer would be positioned between the scrubbing layer and the attachment layer.
The detergent composition and, preferably, the implement of the present invention are compatible with all hard surface substrates, including wood, vinyl, linoleum, no wax floors, ceramic, Formica(copyright), porcelain, glass, wall board, and the like.